Advances in Carbon–Element Bond Construction under Chan–Lam Cross-Coupling Conditions: A Second Decade

Abstract

Copper-mediated carbon–heteroatom bond-forming reactions involving a wide range of substrates have been in the spotlight for many organic chemists. This review highlights developments between 2010 and 2019 in both stoichiometric and catalytic copper-mediated reactions, and also examples of nickel-mediated reactions, under modified Chan–Lam cross-coupling conditions using various nucleophiles; examples include chemo- and regioselective N-arylations or O-arylations. The utilization of various nucleophiles as coupling partners together with reaction optimization (including the choice of copper source, ligands, base, and other additives), limitations, scope, and mechanisms are examined; these have benefitted the development of efficient and milder methods. The synthesis of medicinally valuable or pharmaceutically important nitrogen heterocycles, including isotope-labeled compounds, is also included. Chan–Lam coupling reaction can now form twelve different C–element bonds, making it one of the most diverse and mild reactions known in organic chemistry.1 Introduction2 Construction of C–N and C–O Bonds2.1 C–N Bond Formation2.1.1 Original Discovery via Stoichiometric Copper-Mediated C–N Bond Formation2.1.2 Copper-Catalyzed C–N Bond Formation2.1.3 Coupling with Azides, Sulfoximines, and Sulfonediimines as Nitrogen­ Nucleophiles2.1.4 Coupling with N,N-Dialkylhydroxylamines2.1.5 Enolate Coupling with sp3-Carbon Nucleophiles2.1.6 Nickel-Catalyzed Chan–Lam Coupling2.1.7 Coupling with Amino Acids2.1.8 Coupling with Alkylboron Reagents2.1.9 Coupling with Electron-Deficient Heteroarylamines2.1.10 Selective C–N Bond Formation for the Synthesis of Heterocycle-Containing Compounds2.1.11 Using Sulfonato-imino Copper(II) Complexes2.2 C–O Bond Formation2.2.1 Coupling with (Hetero)arylboron Reagents2.2.2 Coupling with Alkyl- and Alkenylboron Reagents3 C–Element (Element = S, P, C, F, Cl, Br, I, Se, Te, At) Bond Forma tion under Modified Chan–Lam Conditions4 Conclusions

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

“…[85,86] Last but not least, C(sp 3 )-heteroatom couplings of trifluoroborates 2 and boronic acids esters 4 based on the Cumediated Chan-Lam reaction should be mentioned (Scheme 4). [87][88][89][90]…”

Saturated Boronic Acids, Boronates, and Trifluoroborates: An Update on Their Synthetic and Medicinal Chemistry

“…As mentioned above, the Chan-Lam reaction, namely, copper IIpromoted cross-coupling of boronic derivatives with nucleophiles in the presence of a weak base, has become an important tool to construct C-heteroatom bonds over the last two decades. The method was reviewed several times recently; [148][149][150] in the latter review by Lam and co-workers that was just published, the reactions of aliphatic boronic derivatives were discussed in the corresponding sections. Therefore, we shall provide only a brief overview here, followed by a few selected examples.…”

Synthesis of N-Arylcytisine Derivatives Using the Copper-Catalyzed Chan-Lam Coupling

“…Copper-catalyzed Chan-Lam coupling reactions have been used in the synthesis of natural products, , but there are no reports on the use of such methodology for natural product derivatization. Because this methodology holds promise as one of the most efficient synthetic methods for cross-coupling, with the possibility of forming 12 different C element bonds (C–N, C–O, C–S, C–P, C–F, C–C, C–Cl, C–Br, C–I, C–At, C–Se, and C–Te), , we have explored the use of cytisine as the amine coupling partner in the Chan-Lam cross-coupling reaction to include this versatile synthetic tool in the derivatization of natural products.…”